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Nucleophilic substitution reaction of benzyl bromide with N , N ‐Dimethylaniline: Significance of equilibrium cross‐interaction constant
Author(s) -
Lee Ikchoon,
Park Yong Kyun,
Huh Chul,
Lee Hai Whang
Publication year - 1994
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.610071006
Subject(s) - chemistry , dimethylaniline , nucleophilic substitution , equilibrium constant , bromide , reaction rate constant , computational chemistry , substitution (logic) , medicinal chemistry , substitution reaction , constant (computer programming) , photochemistry , organic chemistry , kinetics , physics , quantum mechanics , computer science , programming language
Abstract Kinetic studies on the reversible reactions of benzyl bromides with N , N ‐dimethylanilines were carried out for both the forward ( k f ) and reverse ( k r ) directions. The equilibrium constants, K were calculated using the ratio k f / k r and the equilibrium cross‐interaction constant, ρ e XY was determined. The ρ e XY value was shown to represent a maximum intensity of interactions between substituents X and Y through covalent bonds within a molecule. The normalized values of ρX (ρ nuc ) and ρXY indicate that in the transition state the fractional development or loss of polar and resonance interactions in the benzyl system are imbalanced or non‐perfectly synchronized. In the forward reaction the fractional loss of resonance interaction becomes enhanced, whereas in the reverse reaction the fractional development of resonance interaction lags behind the corresponding changes of polar interactions by ca 45%.